New azo-dyestuffs



United States Patent NEW AZO-DYESTUFFS Hugo Miguel Illy, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Filed Oct. 27, 1958, Ser. No. 769,568 Claims priority, application Switzerland Nov. 1, 1957 8 Claims. (Cl. 260-163) This invention provides azo-dyestutfs which contain at least one group imparting solubility in water, and at least one group of the formula NHOOR NHCOR in which R represents a vinyl or fl-halogenethyl group. As groups imparting solubility in water there may be mentioned, for example, sulfonic acid amide groups, methyl-sulfone groups, and especially acid groups imparting solubility in water such as carboxylic acid or sulfonic acid groups.

The group of the Formula 1 may be bound to the dyestuli molecule through an alkylene or arylene radical, but is preferably bound directly .to an aromatic nucleus of the dyestuif molecule. The dyestuff may contain further substituents, especially substituents not imparting solubility in water, for example, halogen atoms or nitro, acylamino, alkyl or alkoxy groups.

The invention also provides a process for the manufacture of azo-dyestufi's by coupling a diazotized amine with a coupling component, wherein the diazotized amine and coupling component are so chosen that the dyestulf obtained contains at least one acid group imparting solubility in water and at least one group of the Formula 1. Thus, for example, (a) a diazo component containing a group of the Formula 1 may be coupled with any desired coupling component containing at least one group imparting solubility in water, or (b) any desired diazo-component containing at least one acid group imparting solubility in water is coupled with a coupling component containing a group of the Formula 1. For procedure (a) there are advantageously used as diazo-components amines of the formula R C O NH in which A represents a benzene or naphthalene radical which may contain further substituents, for example, an alkyl or alkoxy group or halogen atom, especially a chlorine atom.

As examples there may be mentioned compounds of the following formulae an NHCOR NHCOR NHCOR NH,

( NHCOR NHCOR /NHCOR HiN CH NHCOR SOaH In the above formulae R represents a vinyl or fi-chlorethyl group.

The amines of the Formulae 3 to 8 are new compounds and can be obtained by reducing the corresponding nitrocompounds under conditions such that the acid radicals are not split off, advantageously by catalytic hydrogenation. The nitro-compounds can be obtained, for example, by the process of United States Patent No. 2,475,846, patented July 12, 1949, by Lennart A. Lundb'erg by condensing 1 molecular proportion of a nitroaldehyde with 2 molecular proportions of S-chloropropionic acid amide or of acrylic acid amide in the presence of a strong acid, especially hydrochloric acid or sulfuric acid.

For use in procedure (b) there may be used as diazocomponents the following amino-sulfonic acids:

l-aminobenzene-2-, -3- or -4-sulfonic acid, Z-amino-1-methoxybenzene-4-sulfonic acid, 3-amino-2-hydroxybenzoic acid-S-sulfonic acid, 3amino-6-hydroxybenzoic acid-S-sulfonic acid, 2-aminophenol-4-sulfonic acid, S-acetylamino-2-aminobenzene-l-sulfonic acid, 4-acetylamino-2-aminobenzene-l-sulfonic acid, S-acetylaminoor S-benzoylarnino-2-aminobenzene-l-carboxylic acid, Z-aminobenzoic acid-4- or -5-sulfonic acid, 1-aminonaphthalene-4-, -5-, -6- or -7-sulfonic acid, 2-aminonaphthalene-4-, -6-, -7- or -8-sulfouic acid, l-aminonaphthalene-S 2 6-disulfonic acid, 1-aminobenzene-2:S-disulfonic acid, l-aminonaphthalene-4:8-, -5:7- or -6:8-dis'ulfonic acid, l-(3'- or 4'-aminobenzoyl)-aminobenZene-3-sulfonic acid, 3-aminopyrene-5z8- or -5:l0-disulfonic acid, 4-nitro-4'-aminostilbene-2:2-disulfonic acid, and also O-acyl derivatives of aminonaphthol sultfonic acids, for example, O-acyl derivatives of l-amino-S-hydroxynaphthalene-3:6- or 4:6-disulfonic acid, dehydrothiotoluidine monoor di-sulfonic acid.

Equally suitable diazo components are aminomonoazo dyestuffs containing sulfonic acid groups, which can be prepared, for example, by coupling a diazotized monoacyl derivative of an aromatic diamine with a coupling component containing an aromatic hydroxyl group or a ketomethylene group and subsequent hydrolysis of the resulting acylaminomonoazo dyestuifs, for example the aminomonoazo dyestuffs obtainable by hydrolysis from phenols, naphthols, S-pyrazolones, barbituric acids, hydroxyquinolines, fi-ketocarboxylic acid derivatives and diazotized monoacyldiaminobenzene, monoacyldiaminostilbene disulfonic acids or the like. As diazotizable aminoazo dyestufis may be used also coupling products of one of the specified coupling components containing amino groups with the diazo compounds of the likewise specified aminosulfonic acids.

It is of advantage to couple such starting materials as droxide, to achieve better fixation.

yield aminoazo dyestuffs containing at least two groups imparting solubility in water.

As suitable coupling components may be mentioned: Amines of the benzene or naphthalene series, preferably those which contain at least one group imparting solubility in water for example N-sulfato-ethyl aniline, l-aminonaphthalene-2-, -4-, -6- or -8-sulfonic acid, l-aminonaphthalene-3 :6-disulfonic acid, l-aminonaphthalene-3 :8- disulfonic acid, 2-aminonaphthalene-6:S-disulfonic acid, furthermore compounds containing aromatically bound hydroxyl groups, for example phenols such as l-hydroxy- 2carboxybenzene, and more especially the sulfonic acids of a-naphthol or ,B-naphthol, for example l-hydroxynaphthalene-3-, -4-, -5-, or -8-sulfonic acid, 2-hydroxynaphthalene-4, -5-, -6-, -7- or -8-sulfonic acid, 1:8-dihydroxynaphthalene-3:6-disulfonic acid, Z-hydroxynaphthalene-3z6- or -6:8-disulfonic acid, l-hydroxynaphthalene-3z6- or -3z8-disu1fonic acid, l-amino 8 hydroxynaphthalene-2:4-, -3:6- or -4:6-disulfonic acid, 2-amino- 8-hydroxynaphthalene-3-sulfonic acid, Z-amino-S-hydroxynaphthalene-17-sulfonic acid and the N-acyl derivative of aminonaphthol sulfonic acids in which the acyl radical is an acetyl, propionyl, butyryl, chloracetyl, benzoyl, ortho-, metaor para-chlorobenzoyl, nitrobenzoyl, tertiary butyl benzoyl, 3'- or 4-aminobenzoyl, methanesulfonyl, ethanesulfonyl, para-toluenesulfonyl or chlorobenzenesulfonyl radical or a carbomethoxy or carbethoxy radical such, for example, as l-hydroxy-8-benzoylaminonaphthalene-3:6-disulfonic acid or l-hydroxy-4-amino- 6-benzoylaminonaphthalene-3-sulfonic acid. Equally suitable as coupling components are compounds containing an enolizable keto group, for example fl-ketocarboxylic acid esters or amides capable of coupling in the tar-position, for example acetoacetic acid arylides, pyrazoles, more especially S-pyrazolones capable of coupling in the 4-position, such as 5-pyrazolone-3-carboxylic acid,

1-phenyl5-pyrazolone-3-carboxylic acid,

l-phenyl-3'-amino-5-pyrazolone-3-carboxylic acid,

l-phenyl-3-methyl-5-pyrazolone-2,- 3'- or -4'-sulfonic acid,

1-phenyl-3-methyl-5-pyrazolone-2' 5 -dichloro-4'- sulfonic acid,

l-phenyl 3 methyl-5-pyrazolone-2':5'-disulfonic acid,

l-phenyl-3-methyl-5-pyrazolone-3'-sulfonamide,

Barbituric acids or hydroxyquinolines such as S-hydroxyquinoline or 2:4-dihydroxyquinoline.

When the diazo component contains no group of Formula 1, such a group must be present in the coupling component. For this purpose are particularly suitable amino or hydroxy compounds of the benzene or naphthalene series, for example the amines of the above formulae 3, 6 and 7.

The coupling is advantageously performed in a weakly acid, neutral or alkaline medium, for example a medium rendered alkaline with an alkali metal bicarbonate or carbonate, preferably in the cold.

The dyestuffs obtained by the present process are suitable for dyeing and printing a wide variety of materials, more especially polyhydroxylated fibrous materials such as cellulose and synthetic fibers, for example of polyvinyl alcohol or regenerated cellulose, or natural materials, for example linen or above all cotton. They are suitable for dyeing by the so-called direct-dyeing method as well as for printing or pad-dyeing, in which method the dyestuff is applied to the material to be dyed and fixed thereon by a heat treatment, for example, steaming, in the presence of analkali. It is of advantage to perform the fixation of the dyestufi on the material to be dyed with the aid of a rather strong alkali, for example an alkali metal hy- Good results are aghieved even at pH values above 9 or preferably above 1 The dyeings produced with the dyestuifs of the invenamide or superpolyurethane fibers from a weakly alka-' line bath.

The dyeings obtained with such dyestufls on wool have excellent fastness to washing and fulling.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages are by weight.

Example 1 6.3 parts (0.02 mol) of 3-aminobenzylidene-bis-(pchloropropionyl)-amide are dissolved in 600 parts of water and 6.2 parts of hydrochloric acid of 30% strength and diazotized with 5 parts of 4 N-s'odium nitrite solution at 0 to 5 C. The clear diazo solution is added dropwise to a solution of 4.78 parts of Z-amino-S-naphthol-7-sulfonic acid, 200 parts of water and 7 parts of sodium carbonate, and the mixture is further stirred at the same temperature. On completion of the coupling, the dyestuff is salted out with 30 parts of sodium chloride. It forms a reddish brown powder corresponding to the formula NHCOCHZCHZCI NHCO CHrCHaCl H2N- SOBH and dyes cotton orange tints.

The 3-aminobenzylidene-bis-(fi-chloropropionyl) -amide used in the first paragraph above can be prepared in the following manner;

10.7 parts of j8-chloropropionyl amide (0.1 mol) 6.04 parts of meta-nitrobenzaldehyde (0.04 mol) 6 parts by volume of alcohol, and

3 parts by volume of hydrochloric acid of 37% strength Example 2 2.45 parts (0.01 mol) of 3-aminobenzylidene-diacrylamide are dissolved with heating in 500 parts of water and 4 parts of hydrochloric acid of 30% strength. The resulting solution is rapidly cooled to 0 C. and diazotized with 10 parts of N-sodium nitrite solution The filtered clear solution is run at 0 to 5 C. into a suspension of 2.39 parts of Z-amino-S-naphthol--sulfonic acid, 25 parts of water and 3 parts of hydrochloric acid of 30% strength. Towards the end of the coupling the solution is neutralized with sodium acetate'and the dyestufi is salted out with 25 parts of sodium chloride; it corresponds to the formula NBC 0 CH=CH2 NBC 0 CH=OH2 I SOaH and dyes cotton red tints.

The 3-aminobenzylidene-diacrylamide used as starting material in this example can be prepared as follows:

41.2 parts (0.15 mol) of 3-nitrobenzylidene-bis-acnylamide are dissolved in a mixture of 350 parts of dimethyl 5 formamide and 280 parts of alcohol and hydrogenated with the use of Raney nickel as catalyst. After 10.1 liters of hydrogen have been absorbed, the hydrogenation is discontinued. Evaporation of the solution yields the crystallization from alcohol.

umn III.

crystalline product which melts at 186l87 C. after re- The amines listed in column I of the following table are diazotized as described in this example and then coupled with the coupling components shown in column II to yield dyestuifs which dye cotton the tints listed in col- Dlazo component Coupling component III Tint on cotton S-aminobenzylidene-bis-(B-chloropropionyD- amide NH0 0 CHzOHiCl NHG 0 CHiOHiOl 3-ami nobenzy1idene-bis- (B-chloropropionyl) amlde NHCOCHzCHzCl NHC O CHzCHzCl 3-aminobenzylidene-bis-(fi-chloropropionynamide NHC O CHzCHzCI NHC O CHzCHzOl H-aminobenzylidene-bis- (fi-chloropropionyD- amide /NHCO CHiCHzCl C H NHO O OHaCHiCl 3-aminobenzy1idene-bis-(fi-chloropropionyhamlde NHCOCHgCHzCl NH0 0 CHaCHiCl 3-amiu0benzy1idene-bis-(fi-chloropropionyD- amid NH0 0 OHiCHiCl NHCOCHzCHzCl 4-aminobenzylidene-bis-(fl-chloropropionyD- amide NBC 0 OHiOHiOl NHCOCHzGHzCl A-aminob enzylidene-bis- (B-ohloropropionyD- amide NH0 0 OHzOHzOl HzN C NHOOCH2OH20] 4aminobenzylidene-bis-(fi-chloropropionyD- amide /NHOOOH2OH2C1 NHCOGHiOHnOl 4-aminobenzylidene-bis-(B-chlcropropionybamide NHCOCH2CH2CI NHCOOHzCHiOl 3-aminobenzy1idene-bis- (acrylamide) NHC O CH=CH2 NBC 0 OH=CH2 l-naphthol-(i(4-amino)-benzoylami.no-3-sulfonic acid NHC o-Oami p-acid 1-11aphthol-8-benzoyl-amino-3: (i-dislllfonic acid l-phenyl-3methyl-5-pyrazo1one-4' sulfonic acid 2-amino-8-naphthol-6-sulionic acid 1-pl1enyl-3-methyl-5-pyrazo1one-2: 5-di-sulionic acid l-phenyl-3-metl1yl-5-pyrazolone-2z5-di-chloro-4-sulfonic acid 1-phenyl-3-methyl-5-pyrazolone-2' 5-di-chloro-4-sulionic ncid Reddish yellow.

Yellow.

Red.

Orange.

Scarlet.

Red.

Yellow.

Red.

Reddish yellow.

Yellow.

I II III Diazo component Coupling component Tint on cotton 12 3-aminobenzylidene-bis-(acrylamide) 1naphthol-8-benzoyl-amino-3:6-disulfonic acid Red.

NBC 0 11:0 H2

NHCOCH=OH2 NH: 13 3-amincbenzylidene-bis-(acrylamide) 1-naphthol-8-acetyl-amino-3 o-disulr'onic acid Do.

NBC 0 0 11:0 Hz

NH1 14 3-aminobenzylidene-bis-(acrylamide) l-phenyl-(FY-amino)--pyrazolone-3-carboxylic acid Golden yellow.

NH O O 0 11:0 H3

NHCOOH=CH2 NH: 15 3-aminobenzylidene-bis-(acrylamide) 1-pheny1-(3-sulfamido)-3-methyl-5-pyrazolone Yellow.

NH0 0 GH=CH2 O l NHC O CH=OH2 and forms a violet powder which dyes cotton violet tints by the method described in Example 6.

Example 3 6.36 parts (0.02 mol) of 3-arninobenzylidene-di-( 8- chloro-propionyl)-amide are diazotized as described in Example 2. The clear solution is cooled to 0 C. and added dropwise at 25 C. to a solution of 5.04 parts (0.01 5.78 parts of 2-aminonaphthalene-4:8-disulfonic acid mol) of the symmetrical urea of 2-amino-5-hydroxyna h are diazotized in the usual manner, and the resulting diazo thalene.7-sulfonic acid, 200 parts of water and 5 parts of solution is treated dI'OPWiSB with stirring at 10 sodium carbonate. On completion of the coupling the a Solution of Parts of y -(I dyestuif solution is neutralized with hydrochloric acid chloropropionyD-amide in 200 parts of water and 2 parts and the dyestulf salted out with 15 parts of sodium chloof hydrochloric acid of 30% strength. On completion ride, it corresponds to the formula 40 of the coupling, the dyestulf solution is heated to 60 C.

Example 5 Cl(CH2)2C ONE and forms a pale red powder which dyes cotton scarlet and the dyestuff is salted out with 40 parts of sodium tints. chloride; it corresponds to the formula Example 4 H038 2.45 parts of 4-aminobenzylidene-bis-(fi-chloropropionyl)-arnide are diazotized as described in Example 1, and the reaction mixture is made up to 340 parts by volume with water. 170 parts of this clear diazo soluv /NHCOCH2OHZC1 tion are added dropwise to a suspension of 3.5 parts of H CH 1 amino 8 naphthol 3.6 drsulfomc acid, 200 parts of water 3 NHCOCHQOHZGI and 3 parts of hydrochloric acid of 30% strength at 0 C. While stirring continuously, the hydrochloric acid beand forms a brown Powder Which y Cotton Orange ing cautiously neutralized with sodium acetate (pH=3.5). tints by the method described in Example 6.

On completion of the coupling of the monoazo dyestuff, the solution is rendered alkaline to brilliant red paper with 18 parts of sodium carbonate and mixed with 170 1 part of the dyestutf of Example 6 of the table is parts of the above diazo solution, whereupon the red mixed with 9 parts of urea and dissolved in 100 parts of coloration changes to violet. On completion of the couwater.

pling, the mixture is neutralized with hydrochloric acid This solution is used to impregnate a cotton fabric at and the dye-stuff salted out with 40 parts of sodium 80 C. on the padder, and the surplus liquor is then chloride. The resulting disazo dyestuif corresponds to the squeezed oif until the weight of the fabric shows an in- Example 6 formula crease of NH: OH CICHICHlCOHN l Nuooonlonloi OHON=N- N=NC O CICHECHZOOHN/ \NHCOCH2CH201 The material thus impregnated is dried and then impregnated at room temperature with a solution containing per liter 10 grams of sodium hydroxide and 300 grams of sodium chloride, squeezed to a weight increase of 75% in which B represents a member selected from the group consisting of the sulfobenzene and sulfonaphthalene radicals.

4. The azo-dyestufi of the formula steamed for 60 seconds at 1 to 101 C., rinsed, treated 5 CmHNOC CH=CHI)2 in 0.5% sodium bicarbonate solution, rinsed, soaped for 15 minutes in a boiling 0.3% solution of a non-ionic detergent, rinsed and dried.

A vivid red dyeing fixed fast to boiling results. When CH8 a spun rayon fabric instead of a cotton fabric is treated 10 I as described, a similarly good result is achieved. HO

What is claimed is: \N/ 1. An azo-dyestuif which contains at least one group I imparting solubility in water and which corresponds to 0 the formula RCONH\ G1 HO- AN=N-B SOSH RCONH D hi h A t b 1 t d f th 0 5. The azo dyestuif of the formula in w c represen s a mem er se ec e rom e group consisting of benzene and naphthalene radicals, B rep- CHGINOG OH CH2) resents the radical of a coupling component selected from the group consisting of naphthols, p-aminobenzenes and 5-pyrazolones, and R is a member selected from the OOOH group consisting of vinyl and p-halogenethyl groups, and in which formula the radical of the formula HO RCONH 171 /CH-- RCONH is bound directly to a benzene nucleus which is itself NH: bound directly to the azo linkage.

2. An azo dyestuff which contains at least one group 6. The azo dyestuif of the formula imparting solubility in water and which corresponds to the formula (cwmomoorvnnnoOrr: CH3

0H==0H-00NH Ho 1;

CH N CHFCH-CONH N=N*B in which B represents the radical of a coupling com- 01 ponent selected from the group consisting of naphthols, p-aminobenzenes and S-pyrazolones. S0311 3. An azo dyestutf which contains at least one group The azo dyesmfl of the formula imparting solubility in water and which corresponds to the formula (momomooNHnoH OH NHOCQ ClCHgCHzCONH N=NBSOaH H038 SOBH CICECHMONH 8. The azo dyestufi of the formula (ClGHaCHgOONEaCH 11 H038 NHO o-O-Nni References Cited in the file of this patent UNITED STATES PATENTS 2,126,468 Holzach et al. Aug. 9, 1938 2,158,283 Haddock et al. May 16, 1939 2,200,423 Krebser May 14, 1940 2,274,717 Lyford Mar. 3, 1942 2,398,367 Felix et al. Apr. 16, 1946 2,402,538 Dreyfus June 25, 1946 2,657,205 Heyna et al. Oct. 27, 1953 2,720,517 Kartaschofi Oct. 11, 1955 UNITED sTATDs PATENT OFFICE CERTIFICATE OF CORECTION Patent N0a 2,984,659 May 16 1961 Hugo Miguel 111 It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent. should read as -corrected below.

Column 3, line 21, for "naphthalone-lY-sulfonic" read naphthalene-'I-sulfonic Signed and sealed this 10th day of October 1961..

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Commissioner of Patents Attesting Officer USCOMM-DC' 

1. AN AZO-DYESTUFF WHICH CONTAINS AT LEAST ONE GROUP IMPARTING SOLUBILITY IN WATER AND WHICH CORRESPONDS TO THE FORMULA 